NO162076B - MODIFIED COPOLYMERS OF ETHYLENE, AND CONTINUOUS PROCEDURE FOR THE PREPARATION OF SUCH COPOLYMERS. - Google Patents
MODIFIED COPOLYMERS OF ETHYLENE, AND CONTINUOUS PROCEDURE FOR THE PREPARATION OF SUCH COPOLYMERS. Download PDFInfo
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- NO162076B NO162076B NO824360A NO824360A NO162076B NO 162076 B NO162076 B NO 162076B NO 824360 A NO824360 A NO 824360A NO 824360 A NO824360 A NO 824360A NO 162076 B NO162076 B NO 162076B
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- Prior art keywords
- copolymers
- ethylene
- copolymer
- reactor
- radical initiator
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 58
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000005977 Ethylene Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000004711 α-olefin Substances 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 19
- 150000003254 radicals Chemical class 0.000 claims description 18
- -1 peroxide compound Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 claims description 3
- PZILQNGWHUGDLZ-UHFFFAOYSA-N 2-(2-acetyloxypropan-2-yldiazenyl)propan-2-yl acetate Chemical compound CC(=O)OC(C)(C)N=NC(C)(C)OC(C)=O PZILQNGWHUGDLZ-UHFFFAOYSA-N 0.000 claims description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 abstract 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910010062 TiCl3 Inorganic materials 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KEVMYFLMMDUPJE-UHFFFAOYSA-N 2,7-dimethyloctane Chemical group CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910015227 MoCl3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910010068 TiCl2 Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910012375 magnesium hydride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/50—Partial depolymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Abstract
Description
Oppfinnelsen vedrører kopolymerer som er oppnådd ved å modifisere rå-kopolymerer av etylen og minst ett a-olefin med 3-12 karbonatomer. Den vedrører også en fremgangsmåte for fremstilling av slike kopolymerer. The invention relates to copolymers obtained by modifying crude copolymers of ethylene and at least one α-olefin with 3-12 carbon atoms. It also relates to a method for producing such copolymers.
Det har lenge vært kjent at det er mulig å polymerisere etylen under et svært høyt trykk og ved forhøyet temperatur, i nærvær av en friradikal-initiator. Dette gir en polymer som er kjent under navnet radikal-LD-polyetylen. Uavhengig av dens smelteindeks, så fremviser denne polymer i alminnelighet en noenlunde strekkevne ved fremstilling av rørformede hylstre, It has long been known that it is possible to polymerize ethylene under a very high pressure and at an elevated temperature, in the presence of a free radical initiator. This gives a polymer known under the name radical-LD polyethylene. Regardless of its melt index, this polymer generally exhibits a fair amount of tensile strength in the manufacture of tubular casings,
og en middelmådig rivstyrke. På den annen side gjør den det mulig å oppnå en god boble-stabilitet ved ekstruderingsblåsing og den har en utmerket' fremstillingsevne. Fremstillingsevnen er på den ene side definert som. fravær av forhastet brudd i ekstrudatet ("smelte-brudd") og på den annen side som energien som forbrukes under ekstruderingen. and a mediocre tear strength. On the other hand, it makes it possible to achieve a good bubble stability by extrusion blowing and it has excellent manufacturability. On the one hand, the manufacturing capability is defined as. absence of hasty breakage in the extrudate ("melt breakage") and on the other hand as the energy consumed during extrusion.
Det er blitt oppnådd vesentlige forbedringer av strekkevne og rivstyrke ved fremstilling av kopolymerer av etylen og minst ett a-olefin, så som propylen og but-l-en, i nærvær av et katalysatorsystem av Ziegler-type. Det er imidlertid funnet at under deres ekstruderingsblåsing er boblene ustabile og hullene har en umiddelbar tilbøyelighet til å vokse større i tilfeller med perforering av boblene. Det er også funnet forhastet brudd i ekstrudatet under ekstrudering. Substantial improvements in tensile strength and tear strength have been achieved by preparing copolymers of ethylene and at least one α-olefin, such as propylene and but-1-ene, in the presence of a Ziegler-type catalyst system. However, it has been found that during their extrusion blowing the bubbles are unstable and the holes have an immediate tendency to grow larger in cases of perforation of the bubbles. Hasty breakage in the extrudate during extrusion has also been found.
Fransk patentskrift nr. 2.132.780 beskriver etylen/a-olefin-kopolymerer som er modifisert ved innvirkning, i ekstruderen, French Patent No. 2,132,780 describes ethylene/α-olefin copolymers which are modified by impact, in the extruder,
av friradikal-initiatorer i mengder mellom 0,005 og 5 vekt%, of free radical initiators in amounts between 0.005 and 5% by weight,
med hensyn til polymeren som blir modifisert, ved en temperatur mellom 204 og 345°C under et trykk mellom 14 og 350 bar. with respect to the polymer being modified, at a temperature between 204 and 345°C under a pressure between 14 and 350 bar.
I forhold til polymerene hvorfra de stammer, har alle de således modifiserte polymerer redusert molekylvektsfordeling, smelteindeks som er øket minst 50%, og nedsatt midlere molekylvekt. In relation to the polymers from which they originate, all the polymers modified in this way have a reduced molecular weight distribution, a melting index that is increased by at least 50%, and a reduced average molecular weight.
Britisk patentskrift nr. 1.043.082 beskriver en intim blanding av etylen/a-olefin-kopolymerer med fra 0,001 til 10 vekt% av en friradikal-initiator, ved en temperatur mellom 60 og 300°C, fortrinnsvis i en ekstruder. British Patent No. 1,043,082 describes an intimate mixture of ethylene/α-olefin copolymers with from 0.001 to 10% by weight of a free radical initiator, at a temperature between 60 and 300°C, preferably in an extruder.
BRD-patentskrifter nr. 1.301.540 og nr. 1.495.285 beskriver behandling, mellom 50 og 250°C, av en polyolefin i løsning eller suspensjon i et inert løsningsmiddel, med eh friradikal-initiator (0,005 til 20 vekt% med hensyn til polyolefinet) i nærvær av et sensibiliseringsmiddel (sulfitt, tiosulfat, hydrazin, merkaptan etc). Denne fremgangsmåte tillater at den reduserte viskositet til polyolefinene nedsettes fra 1-20 til 0,3-5. BRD patents No. 1,301,540 and No. 1,495,285 describe the treatment, between 50 and 250°C, of a polyolefin in solution or suspension in an inert solvent, with eh free radical initiator (0.005 to 20% by weight with regard to the polyolefin) in the presence of a sensitizing agent (sulphite, thiosulphate, hydrazine, mercaptan etc). This method allows the reduced viscosity of the polyolefins to be reduced from 1-20 to 0.3-5.
Et formål med oppfinnelsen er å oppnå etylenpolymerer som, ved anvendelse til fremstilling av filmer, samtidig på den ene side har egenskapene til radikal-LD-polyetylen, nemlig boble-stabiliteten og fremstillingsevnen, og på den annen side egenskapene til kopolymerene oppnådd i nærvær av katalysator-systerner av Ziegler-type, nemlig strekkevnen og rivstyrken. An object of the invention is to obtain ethylene polymers which, when used for the production of films, simultaneously have on the one hand the properties of radical-LD polyethylene, namely the bubble stability and manufacturability, and on the other hand the properties of the copolymers obtained in the presence of Ziegler-type catalyst cylinders, namely tensile strength and tear strength.
Rå-kopolymerene som modifiseres for oppnåelse av kopolymerene i henhold til oppfinnelsen, inneholder 0,5-10 mol% enheter som stammer fra a-olefinet med 3-12 karbonatomer, og rå-kopolymerene er fremstilt i nærvær av et katalysatorsystem av Ziegler-type, ved en temperatur på 30-320°C og under et trykk på 1-2500 bar. De erkarakterisert vedbestemt grenseviskositet, smelteindeks, densitet, løselighet og ekstraherbarhet som angitt i krav 1. The crude copolymers which are modified to obtain the copolymers according to the invention contain 0.5-10 mol% of units originating from the α-olefin with 3-12 carbon atoms, and the crude copolymers are prepared in the presence of a catalyst system of the Ziegler type , at a temperature of 30-320°C and under a pressure of 1-2500 bar. They are characterized by determined limit viscosity, melt index, density, solubility and extractability as stated in claim 1.
a-olefinet kan spesielt velges blant propylen, but-l-en, pent-l-en, heks-l-en, mety1-pent-l-en, hept-l-en, okt-l-en eller blandinger derav. The α-olefin can in particular be selected from propylene, but-1-ene, pent-1-ene, hex-1-ene, methyl-1-pent-1-ene, hept-1-ene, oct-1-ene or mixtures thereof.
Uttrykket "målt grenseviskositet n ™" skal forstås som verdien av viskositeten ved skjærkraft-gradient null, oppnådd ved ekstrapolering av kurven til den målte viskositet som funksjon av skjærkraft-gradienten. Målingene blir utført ved hjelp av hvilket som helst egnet utstyr, og spesielt reometerbalansen beskrevet i fransk patentskrift nr. 1.462.343. Målingene blir fordelaktig utført ved den temperatur hvorved smelteindeksen blir målt i overensstemmelse med ASTM standard spesifikasjon D 1238-73, dvs. ved 190°C. The term "measured limiting viscosity n ™" is to be understood as the value of the viscosity at zero shear force gradient, obtained by extrapolation of the curve of the measured viscosity as a function of the shear force gradient. The measurements are carried out using any suitable equipment, and in particular the rheometer balance described in French patent document No. 1,462,343. The measurements are advantageously carried out at the temperature at which the melting index is measured in accordance with ASTM standard specification D 1238-73, i.e. at 190°C.
Uttrykket "beregnet grenseviskositet n " skal forstås som verdien av viskositeten ved skjærkraft-gradient null, oppnådd ved beregning fra molekylvektfordelingen bestemt ved gelgjennom-trengnings-kromatografi (GPC). Teorien til BUECHE (J. Chem. Phys. 1956 (25) 599) viser 'at en lineær polymer, dersom den er iso-molekylær, oppnår et forhold av typen n = K M 3 ' 4, hvor nQ er grenseviskositeten, K er en temperaturavhengig proporsjonalitets-koeffisient og M er den midlere molekylvekt. Dersom polymeren er polydispers, må dette forhold inkludere en reologisk midlere molekylvekt M, som uttrykkes, som funksjon av , vektprosenten, og , molekylvekten av hver fraksjon av polymeren bestemt ved GPC, ved forholdet: The term "calculated limiting viscosity n" is to be understood as the value of the viscosity at zero shear force gradient, obtained by calculation from the molecular weight distribution determined by gel permeation chromatography (GPC). The theory of BUECHE (J. Chem. Phys. 1956 (25) 599) shows 'that a linear polymer, if it is iso-molecular, obtains a relationship of the type n = K M 3 ' 4, where nQ is the limiting viscosity, K is a temperature-dependent proportionality coefficient and M is the average molecular weight. If the polymer is polydisperse, this ratio must include a rheological average molecular weight M, which is expressed, as a function of , the weight percent, and , the molecular weight of each fraction of the polymer determined by GPC, by the ratio:
Ved en temperatur på 190°C oppnås det følgende forhold eksperimentelt for etylen/a-olefin-kopolymerer: At a temperature of 190°C, the following ratio is obtained experimentally for ethylene/α-olefin copolymers:
log n£ = 3,482 logMfc- 13,342. log n£ = 3.482 logMfc- 13.342.
Uavhengig av de modifiserte kopolymerer i henhold til oppfinnelsen, så er således nQ den beregnede grenseviskositet som en etylen/a-olefin-kopolymer med den samme antallsmidlere molekylvekt (Mn), den samme vektsmidlere molekylvekt (Mw) > den samme smelteindeks (MI) og den samme densitet (p) ville ha. Forholdet n o</>n o oppnådd for umodifiserte kopolymerer av etylen og en a-olefin er tilnærmet lik 1, innen grensene for eksperi-mentelle feil. Regardless of the modified copolymers according to the invention, nQ is thus the calculated intrinsic viscosity as an ethylene/α-olefin copolymer with the same number average molecular weight (Mn), the same weight average molecular weight (Mw) > the same melt index (MI) and the same density (p) would have. The ratio n o</> n o obtained for unmodified copolymers of ethylene and an α-olefin is approximately equal to 1, within the limits of experimental error.
Den forbedrede oppførsel av de modifiserte kopolymerer i henhold til oppfinnelsen, under ekstruderingsblåsing av filmer, må tilskrives det faktum at de har et forhold n rn /n c på mellom 1,5 og 10. The improved behavior of the modified copolymers according to the invention, during extrusion blowing of films, must be attributed to the fact that they have a ratio n rn /n c of between 1.5 and 10.
De modifiserte kopolymerer i henhold til oppfinnelsen har en smelteindeks på mellom 0,1 og 10 dg/min og en densitet på mellom 0,910 og 0,955 g/cm<3>. Ved anvendelse for fremstilling av rørformede filmer, det vil si når deres smelteindeks ikke overskrider ca. 3 dg/min, fremviser disse modifiserte kopolymerer en fremstillingsevne som det er verdt å legge merke til, og har utmerkede egenskaper, spesielt en industriell strekkevne, definert som den tykkelse av film som tillater kontinuerlig fremstilling ved ekstruderingsblåsing i en periode på 2 timer uten forstyrrelser, på så lite som 7 pm. The modified copolymers according to the invention have a melt index of between 0.1 and 10 dg/min and a density of between 0.910 and 0.955 g/cm<3>. When used for the production of tubular films, i.e. when their melt index does not exceed approx. 3 dg/min, these modified copolymers exhibit noteworthy manufacturability and have excellent properties, especially an industrial stretchability, defined as the thickness of film that allows continuous extrusion blow molding for a period of 2 hours without interruption , in as little as 7 pm.
De er fullstendig løselige og ekstraherbare i de vanlige They are completely soluble and extractable in the ordinary
løsningsmidler for polyolefiner. solvents for polyolefins.
Fremgangsmåten i henhold til oppfinnelsen, for fremstilling av modifiserte kopolymerer som omtalt ovenfor, hvorved etylen kopolymeres med minst ett a-olefin i minst en reaktor, i nærvær av et katalysatorsystem av Ziegler-type, ved en temperatur på 30-320°C og under et trykk på 1-2500 bar, erkarakterisertved at 0,01-1 milliiriol pr. kg kopolymer, av minst én friradikal-initiator innføres ved slutten av omsetningen, ved en temperatur mellom 220 og 320°C og et trykk mellom 500 og 1000 bar. The process according to the invention, for the production of modified copolymers as discussed above, whereby ethylene is copolymerized with at least one α-olefin in at least one reactor, in the presence of a Ziegler-type catalyst system, at a temperature of 30-320°C and below a pressure of 1-2500 bar, is characterized by 0.01-1 milliiriol per kg copolymer, of at least one free radical initiator is introduced at the end of the reaction, at a temperature between 220 and 320°C and a pressure between 500 and 1000 bar.
En variant av fremgangsmåten i henhold til oppfinnelsen, som utføres kontinuerlig, innebærer kopolymerisering ved 180-320°C og 300-2500 bar, idet katalysatorsystemets midlere oppholdstid i reaktoren er mellom 1 og 120 sekunder, og den erkarakterisert vedat friradikalinitiatoren blir innført i reaktorens siste reaksjonssone eller i den siste reaktor i et sett av seriekoblede reaktorer. A variant of the method according to the invention, which is carried out continuously, involves copolymerization at 180-320°C and 300-2500 bar, with the average residence time of the catalyst system in the reactor being between 1 and 120 seconds, and it is characterized by the fact that the free radical initiator is introduced into the reactor's last reaction zone or in the last reactor in a set of series-connected reactors.
Den maksimale verdi for trykket ved utførelse av fremgangsmåten velges slik at det hindrer polymerisering av den uomsatte monomer og følgelig dannelse av radikal-LD-polyetylen. The maximum value for the pressure when carrying out the method is chosen so that it prevents polymerization of the unreacted monomer and consequently formation of radical LD polyethylene.
Kopolymeriseringen blir utført i minst én reaktor som omfatter minst én reaksjonssone. Reaktoren kan være en autoklav eller en rørformet reaktor med flere reaksjonssoner. Det kan være fordelaktig å anta en spesiell anordning for polymerisasjons-installasjonen, f.eks. en av dem som er beskrevet i de franske patentskrifter nr. 2.346.374 og nr. 2.385.745. a-olefinet blir enten innført eller dannet ved oligomeriseringen av etylen. Andelen av a-olefin i reaksjonsblandingen avhenger av naturen The copolymerization is carried out in at least one reactor comprising at least one reaction zone. The reactor can be an autoclave or a tubular reactor with several reaction zones. It may be advantageous to assume a special device for the polymerization installation, e.g. one of those described in the French patent documents No. 2,346,374 and No. 2,385,745. The α-olefin is either introduced or formed by the oligomerization of ethylene. The proportion of α-olefin in the reaction mixture depends on the nature
til nevnte a-olefin. Den ligger fordelaktig mellom 15 og 35 vekt% når det dreier seg om propylen, mellom 5 og 65 vekt% når det dreier seg om but-l-en og mellom 5 og 80 vekt% når det dreier seg om heks-l-en. Den er ikke nødvendigvis konstant over reaktorlengden. to said α-olefin. It is advantageously between 15 and 35% by weight when it concerns propylene, between 5 and 65% by weight when it concerns but-1-ene and between 5 and 80% by weight when it concerns hex-1-ene. It is not necessarily constant over the reactor length.
Katalysatorsystemet av Ziegler-type omfatter på den ene side minst én aktivator valgt blant hydridene og de organo-metalliske forbindelser av metaller fra gruppene I til III i det periodiske system, og på den annen side minst én halogen-forbindelse av et overgangsmetall fra gruppene IVa til Via, eventuelt festet til en inert bærer eller blandet med en forbindelse av et metall fra gruppe VIII. The Ziegler-type catalyst system comprises, on the one hand, at least one activator selected from the hydrides and the organo-metallic compounds of metals from groups I to III of the periodic table, and on the other hand at least one halogen compound of a transition metal from groups IVa to Via, optionally attached to an inert support or mixed with a compound of a metal from Group VIII.
Aktivatoren kan være: The activator can be:
et alkyl-aluminium, så som triety1-aluminium, tributyl-aluminium, triisobutyl-aluminium eller triokty1-aluminium, an alkylaluminum, such as triethylaluminum, tributylaluminum, triisobutylaluminum or trioctylaluminum,
et klordialkyl-aluminium, så som klordietyl-aluminium, a chlorodialkylaluminum, such as chlorodiethylaluminum,
et dikloralkyl-aluminium, så som dikloretyl-aluminium, a dichloroalkylaluminum, such as dichloroethylaluminum,
et alkylsiloksalan med formelen: an alkylsiloxalane of the formula:
hvor R-jy R2, R^og R4er hydrokarbonradikaler som har fra 1 til 10 karbonatomer, og Rj- enten er et hydrokarbonradikal med fra where R-jy R2, R^ and R4 are hydrocarbon radicals having from 1 to 10 carbon atoms, and Rj- is a hydrocarbon radical with from
1 til 10 karbonatomer eller et radikal av typen 1 to 10 carbon atoms or a radical of the type
En forbindelse omfatter alkylaluminium-fluorid og har formelen (A1R2F) (AlR2X)aeller (AlR2F) (AlR2H)b(AlR3)chvor R er en alkylgruppe med fra 1 til 12 karbonatomer, X er et halogen forskjellig fra fluor, 0,14a < 0,4, 0,1 < b < 0,4 og 0,05 c <? 0,2. A compound comprises alkyl aluminum fluoride and has the formula (A1R2F) (AlR2X)aor (AlR2F) (AlR2H)b(AlR3)where R is an alkyl group with from 1 to 12 carbon atoms, X is a halogen other than fluorine, 0.14a < 0.4, 0.1 < b < 0.4 and 0.05 c <? 0.2.
Halogenforbindelsen av et overgangsmetall fra gruppene IVa til Via, eventuelt festet til en inert bærer eller blandet med en forbindelse av et metall fra gruppe VIII, kan være: The halogen compound of a transition metal from groups IVa to Via, possibly attached to an inert carrier or mixed with a compound of a metal from group VIII, can be:
fiolett titanklorid, TiCl3.|a1C13, violet titanium chloride, TiCl3.|a1C13,
en forbindelse med formelen (TiCl ) (MgCl0) (AlCl,,) (RMgCl), i hvilken 2 ^ a 3, y> 2, O ^ z ^ og 0 < b ^ 1, alene eller blandet med en forbindelse med formelen TiCl3(AlCl3) (E.TiCl^)x i hvilken 0 < w 4 |, 0 < x << 0,03 og E er diisoamyl- eller di-n-butyleter, a compound of the formula (TiCl ) (MgCl0) (AlCl,,) (RMgCl), in which 2 ^ a 3, y> 2, O ^ z ^ and 0 < b ^ 1, alone or mixed with a compound of the formula TiCl3 (AlCl3) (E.TiCl^)x in which 0 < w 4 |, 0 < x << 0.03 and E is diisoamyl or di-n-butyl ether,
et produkt som oppnås ved å bringe en kompleks magnesium-forbindelse, som omfatter minst én forbindelse valgt blant magnesium-monohalogenider og halogen-magnesium-hydrider, i kontakt med et titan- eller vanadium-halogenid i hvilket metallet har en valens på<3 , a product obtained by contacting a complex magnesium compound, comprising at least one compound selected from magnesium monohalides and halogen-magnesium hydrides, with a titanium or vanadium halide in which the metal has a valency of <3,
en forbindelse med formelen (MX ) (MgX„). (RMgX) (HMgX), i a compound of the formula (MX ) (MgX„). (RMgX) (HMgX), i
a£p c q hvilken M er et metall fra gruppene IVa eller Va i det periodiske system, X er et halogen, R er et hydrokarbonradikal, 2^a 3,5, 1 « b < 30, 1^cs< 8 og 0^d < 10, a£p c q which M is a metal from groups IVa or Va in the periodic table, X is a halogen, R is a hydrocarbon radical, 2^a 3.5, 1 « b < 30, 1^cs< 8 and 0^d < 10,
en forbindelse med formelen (TiCl3.|a1C13)(MC13)x(MgX2) y a compound with the formula (TiCl3.|a1C13)(MC13)x(MgX2) y
i hvilken M er et overgangsmetall fra gruppene Va og Via i det periodiske system, X er et halogen, 0 ,3 .< x ~$ 3 og O < y^20, in which M is a transition metal from groups Va and Via in the periodic table, X is a halogen, 0 .3 .< x ~$ 3 and O < y^20,
en forbindelse dannet av blandede krystaller inneholdende TiCl3(eller TiCl2), AlCl3og andre metallklorider så som a compound formed from mixed crystals containing TiCl3 (or TiCl2), AlCl3 and other metal chlorides such as
FeCl2, NiCl2, MoCl3 og MgCl2, FeCl2, NiCl2, MoCl3 and MgCl2,
en forbindelse med formelen (TIK 3 -,) (0 n SiL4. -n )b, i hvilken M er et overgangsmetall fra gruppene IVa til Via i det periodiske system, 0 er en eventuelt substituert aromatisk eller poly-aromatisk kjerne som har fra 6 til 15 karbonatomer, L er enten et halogenatom eller en hydroksy lgruppe, 1 < n<3 og 0,2 b>$ 2, hvor nevnte forbindelse er forbundet, om passende, med AlCl3, MgCl2 og/eller et halogenid av et metall fra gruppe VIII, eller a compound with the formula (TIK 3 -,) (0 n SiL4. -n )b, in which M is a transition metal from groups IVa to Via in the periodic table, 0 is an optionally substituted aromatic or poly-aromatic nucleus having from 6 to 15 carbon atoms, L is either a halogen atom or a hydroxyl group, 1<n<3 and 0.2 b>$ 2, wherein said compound is connected, if appropriate, with AlCl3, MgCl2 and/or a halide of a metal from group VIII, or
en forbindelse med formelen X m-n M(0R) n i hvilken M bety 1r ett eller flere metairer fra gruppene Ia, Ila, Ilb, Illb og Vila i det periodiske system-, X er et enverdig uorganisk radikal, a compound with the formula X m-n M(0R) n in which M means one or more metals from groups Ia, Ila, Ilb, Illb and Vila in the periodic table-, X is a monovalent inorganic radical,
R er et enverdig hydrokarbonradikal, m er valensen til M og R is a monovalent hydrocarbon radical, m is the valence of M and
1^n^m, brakt i kontakt med et halogenderivat eller et overgangsmetall fra gruppene IVa til Via. 1^n^m, brought into contact with a halogen derivative or a transition metal from groups IVa to Via.
Den inerte bærer hvorpå Ziegler-katalysatoren er avsatt, omfatter f.eks. én eller flere av de følgende forbindelser: MgCl2, A1203, Mo03, MnCl2, Si02 og MgO. The inert carrier on which the Ziegler catalyst is deposited comprises e.g. one or more of the following compounds: MgCl2, Al2O3, MoO3, MnCl2, SiO2 and MgO.
Fremgangsmåten i henhold til oppfinnelsen kan utføres ved kopolymerisering av etylen og a-olefinet i nærvær av et mettet hydrokarbon, så som propan, butan eller lignende, anvendt i en mengde på opptil 50 vekt%, først og fremst når temperaturen og/eller trykket er lavt. For å få en nøyaktig kontroll over smelteindeksen til den oppnådde modifiserte kopolymer, kan det også være fordelaktig å utføre kopolymeriseringen i nærvær av opptil 2 mol% hydrogen. The method according to the invention can be carried out by copolymerizing ethylene and the α-olefin in the presence of a saturated hydrocarbon, such as propane, butane or the like, used in an amount of up to 50% by weight, primarily when the temperature and/or pressure is low. In order to obtain a precise control over the melt index of the modified copolymer obtained, it may also be advantageous to carry out the copolymerization in the presence of up to 2 mol% hydrogen.
I henhold til denne første variant blir friradikal-initiatoren innført ved slutten av omsetningen. Denne innføring kan utføres i form av innsprøyting av en løsning eller suspensjon av friradikal-initiatoren inn i den siste reaksjonssone i reaktoren eller settet av reaktorer, eller inn i den siste reaktor av et sett av reaktorer forbundet i serie, og det skal forstås at trykket i nevnte siste sone eller i nevnte siste reaktor er mellom 500 og 1000 bar. According to this first variant, the free radical initiator is introduced at the end of the turnover. This introduction can be carried out in the form of injecting a solution or suspension of the free radical initiator into the last reaction zone of the reactor or set of reactors, or into the last reactor of a set of reactors connected in series, and it is to be understood that the pressure in said last zone or in said last reactor is between 500 and 1000 bar.
I henhold til denne første variant av fremgangsmåten i henhold til oppfinnelsen kan friradikal-initiatoren velges blant organiske peroksyder og benzopinakol. En foretrukket peroksyd- According to this first variant of the method according to the invention, the free radical initiator can be chosen from among organic peroxides and benzopinacol. A preferred peroxide-
forbindelse er di-tert.-butylperoksyd. compound is di-tert-butyl peroxide.
I henhold til en ytterligere variant av fremgangsmåten i henhold til oppfinnelsen kopolymeriseres, i et første trinn, etylen med minst ett a-olefin i minst én reaktor i nærvær av et katalysatorsystem av Ziegler-type ved en temperatur på 30-320°C og under et trykk på 1-2500 bar, eventuelt i nærvær av opptil 2 mol% hydrogen, og i et neste trinn blir kopolymeren som er oppnådd i første trinn, bragt i kontakt med 0,01-1 millimol, According to a further variant of the method according to the invention, in a first step, ethylene is copolymerized with at least one α-olefin in at least one reactor in the presence of a Ziegler-type catalyst system at a temperature of 30-320°C and below a pressure of 1-2500 bar, optionally in the presence of up to 2 mol% hydrogen, and in a next step the copolymer obtained in the first step is brought into contact with 0.01-1 millimol,
pr. kg kopolymer, av minst én friradikalinitiator valgt fra 2,2'-azo-bis(acyloksyalkaner) ved en temperatur på 220-320°C i en periode på 5-2 00 sekunder, i en omformingsmaskin. per kg copolymer, of at least one free radical initiator selected from 2,2'-azo-bis(acyloxyalkanes) at a temperature of 220-320°C for a period of 5-200 seconds, in a reforming machine.
Således kan hvilken som helst kopolymer av etylen og minst ett a-olefin med fra 3 til 12 karbonatomer modifiseres i henhold til denne annen variant. Kopolymeren kan oppnås i gass-fase, Thus, any copolymer of ethylene and at least one α-olefin with from 3 to 12 carbon atoms can be modified according to this second variant. The copolymer can be obtained in gas phase,
i flytende fase eller i løsning i et løsningsmiddel. Som forbindelser av typen 2,2<1->azo-bis(acyloksyalkaner) kan de følgende anvendes: in liquid phase or in solution in a solvent. The following can be used as compounds of the type 2,2<1->azo-bis(acyloxyalkanes):
- 2 , 2'-azo-bis(acetoksybutan) - 2, 2'-azo-bis(acetoxybutane)
- 2 , 2 '-azo-bis(acetoksyisobutan) - 2, 2 '-azo-bis(acetoxyisobutane)
- 2,2'-azo-bis (propionoksypropan) . - 2,2'-azo-bis(propionoxypropane) .
Det er fordelaktig å anvende 2,2<1->azo-bis(acetoksypropan). It is advantageous to use 2,2<1->azo-bis(acetoxypropane).
Omformingsmaskinen (maskin for omforming av kopolymeren) er f. eks. en ekstruder eller en presse, som fremmates under et trykk mellom 1 og 25 bar. Det er velkjent at trykket i ekstruderen kan nå 250 bar, i avhengighet av profilen på ekstruderingsskruen. Det trekk å bringe friradikal-initiatoren i kontakt med kopolymeren i omformingsmaskinen blir fordelaktig utført ved anvendelse ' av en løsning av initiatoren eller av en hovedsats som er tørr-tilvirket. The converting machine (machine for converting the copolymer) is e.g. an extruder or a press, which is advanced under a pressure between 1 and 25 bar. It is well known that the pressure in the extruder can reach 250 bar, depending on the profile of the extrusion screw. The act of bringing the free-radical initiator into contact with the copolymer in the reforming machine is advantageously carried out using a solution of the initiator or of a dry-manufactured master batch.
Formålet med de følgende eksempler er å illustrere oppfinnelsen . The purpose of the following examples is to illustrate the invention.
Eksempel 1 Example 1
En blanding bestående av 60 vekt% etylen og 40 vekt% but-1-en blir kopolymerisert under et trykk på 980 bar i en sylindrisk autoklav-reaktor med et volum på 3 liter, hvilken er delt i tre soner ved hjelp av metallskjermer. Temperaturen er 250°C i den første sone, 258°C i den annen sone og 256°C i den tredje sone. Katalysatorsystemet består av katalysatoren TiCl3.|a1C13.VC13 aktivert med dimetyletyldietylsiloksalan (aktivator A heretter), i et forhold Al/Ti + V = 3, og dette blir innsprøytet i den første og den andre sone. 0,065 millimol di-tert.-butyl-peroksyd pr. kg kopolymer blir innført i den tredje sone i form av en løsning i metylcykloheksan. A mixture consisting of 60% by weight ethylene and 40% by weight but-1-ene is copolymerized under a pressure of 980 bar in a cylindrical autoclave reactor with a volume of 3 liters, which is divided into three zones by means of metal screens. The temperature is 250°C in the first zone, 258°C in the second zone and 256°C in the third zone. The catalyst system consists of the catalyst TiCl3.|a1C13.VC13 activated with dimethylethyldiethylsiloxane (activator A hereafter), in a ratio Al/Ti + V = 3, and this is injected into the first and second zones. 0.065 millimol di-tert.-butyl peroxide per kg of copolymer is introduced into the third zone in the form of a solution in methylcyclohexane.
Bortsett fra mengden av anvendt initiator, i millimol pr. kg kopolymer, er de følgende karakteristikker av den oppnådde modifiserte kopolymer (og av de oppnådde modifiserte kopolymerer i overensstemmelse med', de eksempler som følger) , vist i den medfølgende tabell I: andel av enheter som stammer fra a-olefinet i den oppnådde Apart from the amount of initiator used, in millimoles per kg copolymer, the following characteristics of the obtained modified copolymer (and of the obtained modified copolymers in accordance with', the examples that follow), are shown in the accompanying Table I: proportion of units originating from the α-olefin in the obtained
modifiserte kopolymer, bestemt ved infrarød spektroskopi, i mol%, modified copolymer, determined by infrared spectroscopy, in mol%,
katalytisk utbytte av kopolymerer i kg pr. milliatomgram catalytic yield of copolymers in kg per milliatomogram
titan, titanium,
densitet p i g/cm 3, density p in g/cm 3,
smelteindeks MI i dg/min, målt ved 190°C i henhold til melting index MI in dg/min, measured at 190°C according to
ASTM standard spesifikasjon D 1238-73, ASTM Standard Specification D 1238-73,
grenseviskositet, målt ved 190°C ved hjelp av reometerbalansen beskrevet i fransk patentskrift nr. 1.462.349, og uttrykt i poise, og intrinsic viscosity, measured at 190°C using the rheometer balance described in French patent document No. 1,462,349, and expressed in poise, and
forholdet n<m>/n<c.>the ratio n<m>/n<c.>
o' o OE OE
Eksempel 2 ( sammenligning) Example 2 (comparison)
De anvendte forhold er de samme som i eksempel 1, men det blir ikke innført noe peroksyd i den tredje sone. The conditions used are the same as in example 1, but no peroxide is introduced into the third zone.
Eksempel 3 Example 3
En blanding av 70 vekt% etylen og 30 vekt% but-l-en blir kopolymerisert under et trykk på 600 bar i reaktoren fra eksempel 1, og sonene i denne blir oppvarmet til temperaturer på henholdsvis 185°C, 230°C og 270°C. A mixture of 70% by weight ethylene and 30% by weight but-1-ene is copolymerized under a pressure of 600 bar in the reactor from example 1, and the zones in this are heated to temperatures of 185°C, 230°C and 270° respectively C.
Et katalytisk system som omfatter katalysatoren A catalytic system comprising the catalyst
TiCl3-^ A1C13.2VC13aktivert med aktivatoren A i et forhold Al/Ti + V = 3, blir innsprøytet i de første to soner. TiCl3-^ A1C13.2VC13 activated with the activator A in a ratio Al/Ti + V = 3, is injected into the first two zones.
Det samme katalysatorsystem, hvortil det er blitt tilsatt 0,031 millimol benzopinakol pr. kg kopolymer, blir innsprøytet The same catalyst system, to which 0.031 millimoles of benzopinacol per kg of copolymer is injected
i den tredje sone. in the third zone.
Eksempel 4 Example 4
Etylen blir polymerisert i nærvær av 6 volum% propan i en anordning som omfatter to reaktorer anordnet i serie, hvor den første reaktor omfattende 3 reaksjonssoner holdes ved temperaturer på henholdsvis 200°C, 225°C og 185°C og under et trykk på 1200 bar, og den andre reaktor omfattende 2 reaksjonssoner holdes ved temperaturer på henholdsvis 235°C og 280°C og under et trykk på 900 bar. Katalysatorsystemet, som er identisk med det fra eksempel 1, blir innsprøytet i den første og den tredje sone i den første reaktor. Katalysatoren TiCl^ . ^-AlCl^ . 2VC1-J aktivert med en ekvimolékylær blanding av AlfC^H,-)^og<A>1(C2H5)2C1, i et forhold Al/Ti = 3, blir innsprøytet i den første sone i den andre reaktor. The ethylene is polymerized in the presence of 6% by volume of propane in a device comprising two reactors arranged in series, where the first reactor comprising 3 reaction zones is kept at temperatures of 200°C, 225°C and 185°C respectively and under a pressure of 1200 bar, and the second reactor comprising 2 reaction zones is kept at temperatures of 235°C and 280°C respectively and under a pressure of 900 bar. The catalyst system, which is identical to that from example 1, is injected into the first and third zones of the first reactor. The catalyst TiCl^ . ^-AlCl^ . 2VC1-J activated with an equimolecular mixture of AlfC^H,-)^and<A>1(C2H5)2C1, in a ratio Al/Ti = 3, is injected into the first zone of the second reactor.
0,2 millimol, pr. kg kopolymer, av di-tert.-butylperoksyd oppløst i en blanding av mettede C-^-C-^-hydrokarboner blir innsprøytet i den andre sone i den andre reaktor. 0.2 millimoles, per kg of copolymer, of di-tert-butyl peroxide dissolved in a mixture of saturated C-^-C-^-hydrocarbons is injected into the second zone of the second reactor.
Driftsforholdene og det anvendte katalysatorsystem er The operating conditions and the catalyst system used are
slik at etylen delvis dimeriseres til but-l-en, som kopolymeriseres med etylen for å danne en kopolymer som inneholder 0,6 mol% av enheter som stammer fra but-l-en. so that ethylene partially dimerizes to but-1-ene, which copolymerizes with ethylene to form a copolymer containing 0.6 mol% of units derived from but-1-ene.
Eksempel 5 ( sammenligning) Example 5 (comparison)
En blanding av 55 vekt% etylen og 45 vekt% but-l-en blir kopolymerisert under et trykk på 9 50 bar, i nærvær av 0,1 volum% hydrogen, i reaktoren fra eksempel 1, idet sonene blir holdt ved temperaturer på henholdsvis 250°C, 260°C og 260°C. A mixture of 55% by weight ethylene and 45% by weight but-1-ene is copolymerized under a pressure of 950 bar, in the presence of 0.1% by volume of hydrogen, in the reactor from example 1, the zones being kept at temperatures of respectively 250°C, 260°C and 260°C.
Katalysatoren TiCl^.^ AlCl^^VCl^aktivert med aktivatoren A, i et forhold Al/Ti = 3, blir innført i den første og den andre sone. The catalyst TiCl^.^ AlCl^^VCl^ activated with the activator A, in a ratio Al/Ti = 3, is introduced into the first and second zones.
På en REIFENHAUSER-maskin type B 60 blir 50 pm tykke rørformede filmer ekstrudert ved en temperatur på 240°C og med et blåse-forhold på 2. De følgende egenskaper blir målt og nedskrevet i tabell II: rivstyrke TS (uttrykt i g) i lengderetningen L og i tverr-retningen T, bestemt i henhold til ASTM standard spesifikasjon D-1922-67, On a REIFENHAUSER machine type B 60, 50 pm thick tubular films are extruded at a temperature of 240°C and with a blowing ratio of 2. The following properties are measured and recorded in Table II: tear strength TS (expressed in g) in the longitudinal direction L and in the transverse direction T, determined according to ASTM Standard Specification D-1922-67,
krypegrense CS bestemt i henhold til fransk standard spesifikasjon NF T 51103, creep limit CS determined according to French standard specification NF T 51103,
slagfasthet IS (uttrykt i g) bestemt i henhold til ASTM standard spesifikasjon D 1709-80, impact strength IS (expressed in g) determined according to ASTM standard specification D 1709-80,
industriell strekkevne S (uttrykt i p), industrial tensile strength S (expressed in p),
uklarhet H (uttrykt i %), målt i henhold til standard spesifikasjon E 2421, og turbidity H (expressed in %), measured according to standard specification E 2421, and
forbrukt energi W (uttrykt i KWh/kg). consumed energy W (expressed in KWh/kg).
Eksempel 6 Example 6
Forholdene som anvendes er de samme som i eksempel 5, og 0,1 millimol di-tert.-butylperoksyd (oppløst i metylcykloheksan) pr. kg fremstilt kopolymer blir i tillegg innført i den tredje reaksjonssone. Andelen av hydrogen blir modifisert ved å bringe den på 0,3 volum%, i forhold til blandingen av etylen og buten-l-en, slik at det oppnås en kopolymer hvis densitet er identisk med densiteten til kopolymeren oppnådd i eksempel 5. Den oppnådde modifiserte kopolymer blir ekstrudert under de samme forhold som i eksempel 5. Dens egenskaper er angitt i tabell II. The conditions used are the same as in example 5, and 0.1 millimol di-tert-butyl peroxide (dissolved in methylcyclohexane) per kg of copolymer produced is additionally introduced into the third reaction zone. The proportion of hydrogen is modified by bringing it to 0.3% by volume, relative to the mixture of ethylene and butene-1, so that a copolymer is obtained whose density is identical to the density of the copolymer obtained in Example 5. The obtained modified copolymer is extruded under the same conditions as in Example 5. Its properties are listed in Table II.
Eksempel 7 ( sammenligning) Example 7 (comparison)
De anvendte forhold er de samme som i eksempel 5, men hydrogen er ikke til stede. The conditions used are the same as in example 5, but hydrogen is not present.
Eksempel 8 Example 8
De anvendte forhold er de samme som i eksempel 5, og 0,15 volum% hydrogen er til stede. 0,3 millimol 2,2'-azo-bis-(2-acet-oksypropan) , oppløst i et C-^-C-^-kutt av mettede hydrokarboner, pr. kg kopolymer, blir innsprøytet i ekstruderen. Den modifiserte ekstruderte kopolymer har de karakteristikker som er vist i tabell I. The conditions used are the same as in Example 5, and 0.15% by volume of hydrogen is present. 0.3 millimoles of 2,2'-azo-bis-(2-acet-oxypropane), dissolved in a C-^-C-^ cut of saturated hydrocarbons, per kg copolymer, is injected into the extruder. The modified extruded copolymer has the characteristics shown in Table I.
Eksempel 9 Example 9
0,59 millimol pr. kg av 2,2<1->azo-bis-(2-acetoksypropan), oppløst i et C^2~C^4-kutt av mettede hydrokarboner, blir satt til kopolymeren oppnådd i eksempel 5, i det øyeblikk den føres inn i ekstruderen, ved en temperatur på 240°C. Dette gir en ekstrudert modifisert kopolymer hvis karakteristikker er vist i tabell I. 0.59 millimol per kg of 2,2<1->azo-bis-(2-acetoxypropane), dissolved in a C^2~C^4 cut of saturated hydrocarbons, is added to the copolymer obtained in Example 5, at the moment it is introduced in the extruder, at a temperature of 240°C. This gives an extruded modified copolymer whose characteristics are shown in Table I.
EksemDel 10 Eczema Part 10
Ved innsprøyting i ekstruderen av 0,2 millimol av 2,2'-azo-bis-(2-acetoksypropan) pr. kg kopolymer oppnådd i eksempel 5, i form av en hovedsats som er tørr-tilvirket, basert på den samme kopolymer inneholdende 4000 ppm av denne initiator, blir det oppnådd en modifisert kopolymer hvis karakteristikker er vist i tabell I. By injecting into the extruder 0.2 millimoles of 2,2'-azo-bis-(2-acetoxypropane) per kg of copolymer obtained in example 5, in the form of a main batch which is dry-manufactured, based on the same copolymer containing 4000 ppm of this initiator, a modified copolymer whose characteristics are shown in table I is obtained.
Eksempel 11 Example 11
Under de driftsforhold som er beskrevet i eksempel 1, Under the operating conditions described in example 1,
blir det kopolymerisert en blanding av 75 vekt% etylen og 25 vekt% but-l-en, som også omfatter 0,4 volum? hydrogen. Di-tert.-butylperoksyd, oppløst i metylcykloheksan, blir innført i den tredje reaktorsone i en mengde på 0,1 millimol pr. kg kopolymer. Karakteristikkene til kopolymeren som er modifisert på den måte, er vist i tabell I. is a mixture of 75% by weight ethylene and 25% by weight but-1-ene copolymerized, which also comprises 0.4 volume? hydrogen. Di-tert.-butyl peroxide, dissolved in methylcyclohexane, is introduced into the third reactor zone in an amount of 0.1 millimol per kg copolymer. The characteristics of the copolymer thus modified are shown in Table I.
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8124217A FR2519007B1 (en) | 1981-12-24 | 1981-12-24 | MODIFIED COPOLYMERS OF ETHYLENE AND AT LEAST ONE A-OLEFIN AND PROCESS FOR THEIR PREPARATION |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO824360L NO824360L (en) | 1983-06-27 |
| NO162076B true NO162076B (en) | 1989-07-24 |
| NO162076C NO162076C (en) | 1989-11-01 |
Family
ID=9265396
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO824360A NO162076C (en) | 1981-12-24 | 1982-12-23 | MODIFIED COPOLYMERS OF ETHYLENE, AND CONTINUOUS PROCEDURE FOR THE PREPARATION OF SUCH COPOLYMERS. |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US4486579A (en) |
| EP (1) | EP0083521B1 (en) |
| JP (1) | JPS58117201A (en) |
| AT (1) | ATE18412T1 (en) |
| AU (1) | AU568288B2 (en) |
| BR (1) | BR8207479A (en) |
| CA (1) | CA1208399A (en) |
| CS (1) | CS244918B2 (en) |
| DE (1) | DE3269745D1 (en) |
| DK (1) | DK571482A (en) |
| ES (1) | ES518537A0 (en) |
| FI (1) | FI72983C (en) |
| FR (1) | FR2519007B1 (en) |
| GR (1) | GR77081B (en) |
| IE (1) | IE53825B1 (en) |
| IN (1) | IN158055B (en) |
| NO (1) | NO162076C (en) |
| PT (1) | PT76018B (en) |
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| JPS58225106A (en) * | 1982-06-24 | 1983-12-27 | Mitsubishi Petrochem Co Ltd | Preparation of polyethylene |
| US4789714A (en) * | 1983-06-15 | 1988-12-06 | Exxon Research & Engineering Co. | Molecular weight distribution modification in tubular reactor |
| FR2547585B1 (en) * | 1983-06-15 | 1985-09-27 | Charbonnages Ste Chimique | MODIFIED COPOLYMERS OF ETHYLENE AND AT LEAST ONE A-OLEFIN AND PROCESS FOR THEIR PREPARATION |
| US5013801A (en) * | 1983-06-15 | 1991-05-07 | Charles Cozewith | Molecular weight distribution modification in a tubular reactor |
| KR900008459B1 (en) * | 1984-12-14 | 1990-11-22 | 엑손 리서치 앤드 엔지니어링 컴패니 | Molecular weight distribution modification in tubular reactor |
| CA1340037C (en) * | 1985-06-17 | 1998-09-08 | Stanley Lustig | Puncture resistant, heat-shrinkable films containing very low density polyethylene copolymer |
| US5256351A (en) * | 1985-06-17 | 1993-10-26 | Viskase Corporation | Process for making biaxially stretched, heat shrinkable VLDPE films |
| FR2592051B1 (en) * | 1985-12-24 | 1988-10-14 | Charbonnages Ste Chimique | COMPOSITIONS OF ETHYLENE POLYMERS, A PROCESS FOR THEIR PREPARATION AND THEIR APPLICATION FOR OBTAINING INDUSTRIAL ARTICLES |
| DE3642266A1 (en) * | 1986-12-11 | 1987-04-23 | Rauer Kurt | DEGRADATION OF POLYETHYLENE BY MEANS OF RADICAL IMAGES |
| FR2614897B1 (en) * | 1987-05-07 | 1991-12-20 | Charbonnages Ste Chimique | THERMOPLASTIC COMPOSITIONS CONTAINING A MODIFIED ETHYLENE POLYMER AND A C3-C12 OLEFIN POLYMER, THEIR PREPARATION PROCESS AND THEIR APPLICATION FOR OBTAINING INDUSTRIAL ARTICLES |
| US4981605A (en) * | 1987-06-08 | 1991-01-01 | Mitsui Petrochemical Industries, Ltd. | Liquid modified ethylenic random copolymer and its uses |
| JPH0759032B2 (en) * | 1988-01-19 | 1995-06-21 | 富士ゼロックス株式会社 | Image forming device |
| EP0374666B1 (en) * | 1988-12-23 | 1994-01-26 | Bayer Ag | Continuous process for the manufacture of terpolymers of ethylene and vinyl esters |
| US5110870A (en) * | 1989-01-06 | 1992-05-05 | Mitsubishi Kasei Corporation | Extensible film or sheet and process for producing the same |
| US6025448A (en) * | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
| US6538080B1 (en) | 1990-07-03 | 2003-03-25 | Bp Chemicals Limited | Gas phase polymerization of olefins |
| FR2680370B1 (en) * | 1991-08-14 | 1993-11-05 | Enichem Polymeres France Sa | PROCESS FOR THE GRAFTING IN THE LINE OF ACIDS AND ANHYDRIDES OF UNSATURATED CARBOXYLIC ACIDS ON ETHYLENE POLYMERS AND INSTALLATION FOR CARRYING OUT SAID PROCESS. |
| US5674342A (en) * | 1991-10-15 | 1997-10-07 | The Dow Chemical Company | High drawdown extrusion composition and process |
| US5278272A (en) | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
| US5525695A (en) | 1991-10-15 | 1996-06-11 | The Dow Chemical Company | Elastic linear interpolymers |
| US5783638A (en) * | 1991-10-15 | 1998-07-21 | The Dow Chemical Company | Elastic substantially linear ethylene polymers |
| US5395471A (en) * | 1991-10-15 | 1995-03-07 | The Dow Chemical Company | High drawdown extrusion process with greater resistance to draw resonance |
| US5582923A (en) * | 1991-10-15 | 1996-12-10 | The Dow Chemical Company | Extrusion compositions having high drawdown and substantially reduced neck-in |
| IT1266647B1 (en) * | 1993-10-29 | 1997-01-09 | Ausimont Spa | PROCESS OF (CO) POLYMERIZATION OF FLUORINATED OLEPHINE MONOMERS IN AQUEOUS EMULSION |
| US5773106A (en) * | 1994-10-21 | 1998-06-30 | The Dow Chemical Company | Polyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulus |
| US5589551A (en) * | 1995-02-22 | 1996-12-31 | Mobil Oil Corporation | Swell reduction of chromium catalyzed HDPE resins by controlled degradation using high temperature peroxides |
| ITMI20030629A1 (en) * | 2003-03-31 | 2004-10-01 | Polimeri Europa Spa | ELASTOMERIC COMPOSITION FOR THE INSULATION OF ELECTRIC CABLES. |
| BR112013013634B1 (en) * | 2010-12-03 | 2020-11-10 | Dow Global Technologies Llc | process for forming an ethylene-based polymer composition, polymer composition, composition, article |
| CA2834800C (en) * | 2011-07-22 | 2018-10-30 | Elantas Pdg, Inc. | Low temperature cure using benzopinacol polymerization initiator |
| US9593173B2 (en) * | 2014-02-28 | 2017-03-14 | Elantas Pdg, Inc. | Low temperature cure polymerization initiator |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1204826B (en) * | 1957-08-12 | 1965-11-11 | Ruhrchemie Ag | Process for the production of polyethylene or polypropylene |
| GB918182A (en) * | 1960-12-01 | 1963-02-13 | Horstmann & Sherwen Ltd | Improved flexible sealing device for use between telescoping elements |
| DE1301540B (en) * | 1963-01-09 | 1969-08-21 | Chemische Werke Huells Ag | Process for lowering the molecular weight of polyolefins |
| NL298986A (en) * | 1963-01-09 | 1900-01-01 | ||
| DE1495285C3 (en) * | 1963-03-02 | 1975-07-03 | Chemische Werke Huels Ag, 4370 Marl | Process for lowering the molecular weight of polyolefins |
| FR1386006A (en) * | 1963-03-21 | 1965-01-15 | Montedison Spa | Process for purifying polyolefins by removing catalyst residues from them |
| US3325442A (en) * | 1963-03-25 | 1967-06-13 | Monsanto Co | Preparation of polyethylene compositions containing carbon black and peroxide curingagent |
| GB988846A (en) * | 1964-02-05 | 1965-04-14 | Sun Oil Co | Processing of ethylene-propylene copolymer |
| GB1205635A (en) * | 1967-05-12 | 1970-09-16 | Ici Ltd | Polymerisation of ethylene |
| US3862265A (en) * | 1971-04-09 | 1975-01-21 | Exxon Research Engineering Co | Polymers with improved properties and process therefor |
| CA993592A (en) * | 1971-04-09 | 1976-07-20 | Thomas J. Grail | Polymers with improved properties and process therefor |
| US3953655A (en) * | 1972-04-03 | 1976-04-27 | Exxon Research And Engineering Company | Polymers with improved properties and process therefor |
| US4001172A (en) * | 1972-04-03 | 1977-01-04 | Exxon Research And Engineering Company | Polymers with improved properties and process therefor |
| DE2557653A1 (en) * | 1975-12-20 | 1977-06-30 | Basf Ag | PROCESS FOR PRODUCING ETHYLENE POLYMERISATES IN A TWO-ZONE TUBE REACTOR AT PRESSURES ABOVE 500 BAR |
| FR2346374A1 (en) * | 1976-03-31 | 1977-10-28 | Charbonnages Ste Chimique | PERFECTED PROCESS FOR POLYMERIZATION OF ETHYLENE UNDER HIGH PRESSURE |
| US4061694A (en) * | 1976-12-21 | 1977-12-06 | Dart Industries Inc. | Low temperature impact strength molding compositions |
| JPS5952643B2 (en) * | 1977-01-27 | 1984-12-20 | 三井化学株式会社 | ethylene copolymer |
| DE2801541A1 (en) * | 1978-01-14 | 1979-07-19 | Hoechst Ag | AETHYLENE COPOLYMERS AND THEIR USE FOR THE PRODUCTION OF FILMS |
| US4390677A (en) * | 1978-03-31 | 1983-06-28 | Karol Frederick J | Article molded from ethylene hydrocarbon copolymer |
-
1981
- 1981-12-24 FR FR8124217A patent/FR2519007B1/en not_active Expired
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1982
- 1982-04-26 IN IN323/DEL/82A patent/IN158055B/en unknown
- 1982-12-10 GR GR70041A patent/GR77081B/el unknown
- 1982-12-14 AT AT82402276T patent/ATE18412T1/en not_active IP Right Cessation
- 1982-12-14 EP EP82402276A patent/EP0083521B1/en not_active Expired
- 1982-12-14 DE DE8282402276T patent/DE3269745D1/en not_active Expired
- 1982-12-22 CA CA000418365A patent/CA1208399A/en not_active Expired
- 1982-12-22 FI FI824413A patent/FI72983C/en not_active IP Right Cessation
- 1982-12-22 CS CS829555A patent/CS244918B2/en unknown
- 1982-12-22 PT PT76018A patent/PT76018B/en unknown
- 1982-12-23 ES ES518537A patent/ES518537A0/en active Granted
- 1982-12-23 NO NO824360A patent/NO162076C/en unknown
- 1982-12-23 DK DK571482A patent/DK571482A/en not_active Application Discontinuation
- 1982-12-23 BR BR8207479A patent/BR8207479A/en not_active IP Right Cessation
- 1982-12-23 JP JP57235095A patent/JPS58117201A/en active Granted
- 1982-12-23 AU AU91893/82A patent/AU568288B2/en not_active Ceased
- 1982-12-23 IE IE3082/82A patent/IE53825B1/en not_active IP Right Cessation
- 1982-12-27 US US06/453,701 patent/US4486579A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FI72983B (en) | 1987-04-30 |
| FR2519007A1 (en) | 1983-07-01 |
| ES8405041A1 (en) | 1984-05-16 |
| IN158055B (en) | 1986-08-23 |
| ES518537A0 (en) | 1984-05-16 |
| IE53825B1 (en) | 1989-03-01 |
| CA1208399A (en) | 1986-07-22 |
| JPS58117201A (en) | 1983-07-12 |
| NO824360L (en) | 1983-06-27 |
| FI72983C (en) | 1987-08-10 |
| DE3269745D1 (en) | 1986-04-10 |
| JPH0534362B2 (en) | 1993-05-21 |
| AU568288B2 (en) | 1987-12-24 |
| PT76018A (en) | 1983-01-01 |
| FR2519007B1 (en) | 1985-12-27 |
| FI824413L (en) | 1983-06-25 |
| EP0083521A1 (en) | 1983-07-13 |
| GR77081B (en) | 1984-09-06 |
| AU9189382A (en) | 1983-06-30 |
| CS244918B2 (en) | 1986-08-14 |
| ATE18412T1 (en) | 1986-03-15 |
| IE823082L (en) | 1983-06-24 |
| BR8207479A (en) | 1983-10-18 |
| US4486579A (en) | 1984-12-04 |
| PT76018B (en) | 1985-07-26 |
| EP0083521B1 (en) | 1986-03-05 |
| FI824413A0 (en) | 1982-12-22 |
| DK571482A (en) | 1983-06-25 |
| NO162076C (en) | 1989-11-01 |
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